whitney



May 2, 1961 w. B. WHITNEY 2,982,728

LUBRICATING ADDITIVE Filed March 26, 1954 fsoLvENT INVENTOR. 1W. B.WHITNEY ATTORNEYS 2,982,728 Patented May 2, 1961 United States PatentOice This inventionrelates to lubricating additives having detergentand/ orI dispersant properties. Inone of its more specific' aspects,'this invention relates to petroleum lubricating oil compositions. Inanother of its more specific aspects; this invention relates to methods`of pro-- ducing these lubricant additives.

As the speed and output of internal combustion engines have increased tohigher and higher values, the ability of oils Without additives tomaintain an engine free from lacquer, sludge and carbon deposits hasdecreased. Under present day conditions, lubricating oils for use inautoomotive and diesel engines require the use of additive agents. Stopand go driving in cold weather also.- has a tendency to produce sludgein the lubricating system yand additives are necessary to combat thisproblem.

The requirements desirable in a satisfactoryY detergent additive are:(1) compatibility with lubricating oil and other types of additiveswhich may be present; (2) maintenance of satisfactory cleanliness ofengineparts, principally in the ring belt zone of the piston; and` (3)chemi cal inertness with respect to supplemental additives and metalengine parts. Additional desirable characteristics include: (l) ease ofhandling, either as such or as an oil concentrate;-(2) minimum effect onvoil properties, such as viscosity, color and odor; (3) inexpensiveoverall cost; and (4) independence with respect to critically lirnitedor expensive raw materials. Y

The use of additives in lubricating compositions as corrosioninhibitors, oxidation inhibitors, viscosity index improvers, dispersingagents, pour-point depressants, extreme pressure agents, lubricityimprovers and ash forming detergents, is Well known. The need foradditives to improve various specific properties of lubricating oils isall the more'acute and necessary, in view of the service conditionswhich lubricating oils undergo and must withstand. In internalcombustion engines, it is desirable that the lubricating compositions beresistant to sludge and varnish for-mation and in the event of suchformation to prevent the deposition of these materials on the metalliclparts of thevengines.

Each of the'l objects of vthis invention will be obtained by at leastone of the aspects of this invention.

An object of this invention is to provide improved lubricant additiveshaving detergent and/or dispersant properties.

Another object of this invention is to provide new` lubricatingcompositions containing the additives' of this invention.

Accompanying and forming a part of this specification is a drawing whichillustrates apparatus which can be used in the practice of thisinvention.

I have now discovered that an additive for lubricating oils which isuseful as a detergent or dispersant therein fcan be produced bysubjecting a selected hydrocarbon fraction having at least 40 carbonatoms per molecule to oxidation in the presence of alkaline earthcompounds or by oxidizing such a hydrocarbon fraction and thereaftertreating the oxidized material with alkaline earth metal compounds.`

The additives prepared according to' this invention arereadilyincorporated in lubricating oils to form compositions of improvedperformance characteristics. Lubricants containing these additivesexhibit excellent resistance to deposition of sludge and varnish ininternal combustion engines operating both under high performanceconditions and under intermittent service. .They materially reducering-sticking, piston varnish, etc., in such engines ahdjmpartcleanliness to the engine.

AOne material'well suitedy for the production-of my 'i detergent ispreferably one which is substantially satuof between 1.440 and 1.520.Hydrocarbon materials whichjc anj ,be satisfactorily used inthepreparation of my Vdetergent. include substantially saturated dienepoly.

rated 'containing at least 40 carbon atoms per molecule,l

preferably. between 40 and 80 carbon atoms per molecule. The hydrocarbonmaterial should have a refractive index mers, such 'as polybutadiene andpolypentadiene, and polymers of'olens having from 2 to l2 carbon atoms,per

molecule, such as polypropylene, polyethylene, polyiso-y butylene, etc.,preferably having a ratio ot carbon atoms to olefin bondsof at least 40to 1 and not less thank 16 to l, copolymers such as styrene-olefincopolymers, alkylated polystyrene, and a petroleum lubricating oilfraction, which has substantiallyno asphalt, either in its natural stateor 'when deasphalted, and which has beenv solvent extracted to reducedthe content of aromatic-type hydrocarbons therein and preferablydewaxed.

` r.the detergent-type lubricating voil additives of this i.n'vennon'can be used alone or in combination with other` "additivesinfrared spectrograms of these materials reveal the presence of groupscharacteristic of substantially neutralcompletelyorganic,oxygen-containing compounds` such as alcohols, ethers, esters, lactones,anhydrides, ketones, and aldenydes. Examination of the oxidizedmaterials by infrared spectroscopy discloses very marked changes in theabsorption bands upon oxidation of the selected hydrocarbon fractionsdisclosed herein. Astrong carbonyl yband' Within the 5.75 to 5.87 micronregion is producedin the initial oxidation of the hydrocarbon as isAnother object of this invention is to provide a rneth-A I positionspossessing excellent detergent properties.

Other and further objects of this invention will be,

apparent to.those skilled in the art upon studyingthe accompanyingdisclosure.

provide a methj a weak absorption band at 2.94 to about 3.0,micronswhich indicates the presence of a low concentration ofA hydroxyl groups.These bands are characteristic of a concentrated oxidized product butalso appear. in the scanning of the total oxidized hydrocarbon fraction.The concentrated oxidized material also exhibits a broad absorption`band in the'lV to lO'micron region, this band being' much weaker fortheunconcentrated material.

Petroleum fractions whichare suitable for production of the material ofthis invention, i.e., an excellent deter.

gent .lor use in ylubricating oils, include Pennsylvania, Mid-Continent,California, East Texas, Gulf Coast, Venezuela, Borneo, and Arabian.crudeSL The source of the crude from which the petroleum fraction isderived does not significantly vinfluence thepreparationor properties iot the detergent material of this invention, rprovided the petroleumfraction hasbeen prepared by subjecting the crude to certain necessarytreatments to exclude undesired materials therefrom. Y

In the preparation of the preferred petroleum Vfraction from which thedetergent material of this invention is produced, a crude oil -istopped, i.e., distilled to remove therefrom the more volatile, lowermolecular Weight hydrocarbons, such, as gasoline and light gasoil, andthen vacuum reduced to remove heavy gas oil and light lubricating oil ofthe SAE and 20 viscosity grade. Thevacuum reduced crude is then propanefractionated to remove an overhead fraction of about l0() SUS at 210 F.viscosity and the residual material is subjected to a second propanefractionationto 'remove another overhead fraction of about 200 SUS at210 F. viscosity. The residue from the second fractionation may besubjected to a third propane fractionation to remove still anotheroverheadlfractiogn of' about 575 SUS at 210 F. viscosity. Propanefractionation maybe modiied by the presence of butane, ethane or methaneto the extent desired.

Following the propane fractionation step, theoverhead oil fraction issolvent extracted withV a Vselective solvent which Will separate theparai'nic hydrocarbons from the moreV aromatic-type hydrocarbons.Suitable selective solvents for aromatichydrocarbons include amongothers, the various phenols, sulfur dioxide, furfural and/8,dichlorodiethyl ether. This solvent extraction step for the removalof the more highly aromatic compounds can be carried out in accordancewithl the well-knownconcurrent or'countercurrent solvent extrac-vtion'techniques, aswell as by the Duo-Sol technique.

' The resulting solvent extracted material, before vor after theremovalof the more aromatic hydrocarbons,K4

is preferably devvaxed. D'ewaxing may be carried` ont by anyconventional method,ve.g., by solvent dewaxing' using propane or solventmixtures, such as methyl ethyl, ketone ormethy'l isobutyl ketone Awithbenzene at a suitj` able temperature.

EachV fraction of lthe phenol extracted, dewaxed, propane-fractionatedoil can be used in`preparing the detergent material Vofthisv inventionwith good results butv the oil fraction from the vsecond propanefractionation is preferred. It Will be recognized by those skilled inthe art Vthat propane fractionated oils differing from those describedmay bev used or a single broad viscosity cut can be used. The residualmaterial from the iinal propane fractionation contains therejectedasphalt and more aromaticoils.

Although the preferred method for preparation' of feed y stock is asabove described, other methods may be used to secure a similar typehydrocarbon fraction. Thus, a

vacuum'reduced crude which has essentially' no asphalt,l

such as a Pennsylvania oil, mayA be` used directly or after a lightacidY treatment. Another method, Ywhile not feasible 'commercially atthe present time, is ultra-high vacuum (molecular) dis'tillationtoobtain the desired' fraction.

As pointed out above, a polydiene, such as'liquid`poly-- butadiene whichis prepared by sodium-catalyzed 'polymerization of butadiene `and` whichmaterial is subsequently hydrogenated so as to reduce the oleti'nicvun-V carriedout `by Vmeans ofthe process set forthY in U.S;l

Patent No. 2,631,175; issued March 10, 1953, by W. W;

Crouch.

Another suitable feed -stock is a liquid` or semi-solid polybutadiene`which is prepared by conventional emulsion polymerization andcoagulationY to form syntheticrubber, subsequently hydrogenating saidmaterial soV as to reduce the oleiinic unsaturation thereof to thedesired amount and finally. thermally depolymerizing it. suffi- TABLE If Property Broad range Preferred Y Rango Refractive Index m20 1. 440-1.520 1. 4801. 515 Average Moec'ilar Weight above 550 SOO-10, 000-Minirnurn Molecular Weigh 4.50 Viscosity, SUS at 210 F; above50 above100 Viscosity Index (when determinable) 1 50-125 80-120 Carbon AtomContent per Molecule above 40 50-720 present. Hence the viscosity is notdecreased to anyv catalyst, as more `fully disclosed inl U.S..application Seriall No. 333,576, tiled January 23, 19.53, now aban`cloned, by John P. Hogan and Robert L. Banks. Another suitable feedmaterial is -a copolymer -of styrene with oleiins in which the olefinportion constitutes at least 50 percent of the total molecular Weight ofthe molecule. With any of these feed materials, it is desired to reducethe amount of olenic unsaturation to such an extent ythat the ratio ofcarbon atomsto oleiinic bonds ispreferably at leasty 40 :l and not lessthan 16 :1. The hydrocarbon stocks which are useful in the practice ofthis invention include those materials which are identiiable as havingthe following properties set forth in Table I.

lVscosty index notl determinable for non-Newtonian materials.

Lubricating oils which are suitable as feed stock my process have theproperties set forth in` Table II.

DuringY oxidation, scission takes place Ain the large hydrocarbonmolecules, the lighter products'r being col-- lected in traps. Whennitrogen gas was passed through the untreated oil at 250 C.substantially no Volatile products were collected. Only a very smallamount wasr collected when the temperature was raised.to300 C., thusdemonstratingthat the major cause of the formation of the volatileproducts is oxidation and v.not thermal decomposition nor stripping oflight ends,` originally presentv in the oil. With oils ofmoderate."molecular` Weight, scission cannot ytake placein anypositionbut whatv one or Aall of the fragments is sufficiently' small thatdistillation takes place, thus preventing accumulation of` moleculesappreciably smaller. than those originally great extent. Concomitantwith the` oxidative scission reaction, there is a polymerization orcondensationk reaction resulting in an increase in viscosity, The netchange in viscosity is` apparently due Vto the relative magnitude ofeach reaction. In very high molecular Weight hydrocarbons, the oxidativescissionmore frequently results in fragments too large to be removedby-distillation and,

hence, the average molecular weight decreases, tendingl to cause adecrease in viscosity. As the oxidation reacf tion proceeds, thereactions Vcausing. increased molecular weight may overcome, more or.less, .thosecausingl a decrease in molecular Weight.

As ,a result, the molecular.v

lower range tend to increase and those in the higher range tend to`decrease during the initial oxidation period.

If desired, the' p'etroleumvoil fraction which has been highly refined,as described above, may be further subjected to additional refiningtreatments. For example, these petroleum fractions may be hydrogenatedto' convert any aromatic compounds therein to the correspondingnaphthenic -and saturated hydrocarbon', or if desired, these petroleumfractions may be subjected to contact with adsorbents such as silica gelfor the preferential adsorption and removal of the more aromatichydrocarbons therefrom. Generally, the petroleum fraction which isoxidized for the production of the detergent of this invention shouldcontain' not more than 20 percent of the carbon atoms in aromatic'rings, as determined by the ring .analysis described in the book Aspectsof the Constitution of Mineral Oils by K. Van Nes and H. A. Van Westen,Elsevier Press, New YorkY City, NewYork. Itis preferred that thearomatic content of the petroleum fraction lbe reduced to -aneconomically feasible extent by refining procedures sincevoxidation ofaromatic-type hydrocarbons tends to result in the 'formation ofoil-insoluble products not suitablev for the present invention. It alsoappears that aromatic vconstituents oxidize more readily than do thenon-aromatic components. Thus, failure to remove materials containing ahigh percentage of carbon atoms in aromatic rings from the feed beforeoxidation results in formationrof considerable oil-insoluble materials.Usually, a suitable petroleum fraction, upon distillation under'reducedpressure, e.g., molecular distillation, will produce a first percent byweight fraction which has a viscosity of more than 50 SUS at 210 F.,preferably more than 80 SUS at 210 F.

In one method of carrying out my invention, the hydrocarbon fraction isoxidized and then treated with the alkaf line earth compound. During theoxidation reaction, the

hydrocarbon fraction is modified, resulting in a product of increaseddispersing activity which differs from the starting material in respectto the following four physical characteristics: (1) an increase in -thecarbon to hydrogen weight ratio; '(2) usually an increase in molecularweight; (3) an increase in the oxygen content; and (4) a decreasedsolubility in propane under propane fractionating conditions.

All these changes are brought about by contacting an above-describedselected hydrocarbon fraction under suitable conditions of temperatureand pressure withan oxidizing agent, such as free-oxygen, sulfurtrioxide, nitrogen dioxide, nitrogen trioxide, nitrogen pentoxide,acidied chromium oxides and chromates, permanganates, peroxides, such ashydrogen peroxide, sodium peroxide and ozone. Any oxygen-containingmaterial capable of releasing free oxygen under the oxidizing conditionscan be used. Nitric lacid can be used. Other suitable oxidizing agentsinclude air,.relatively pure commercial grade oxygen, oxygen enrichedair,'and a mixture of oxygen with an inert gas, such as carbon dioxideand nitrogen. Even oxygen admixed with natural Igas or methane issatisfactory. Air having less than the usual amount of oxygen may alsobe used. Air is economically a preferred oxidizing agent.

Generally, the oxidation reaction is carried out at a temperature in therangeof from 40 F. to 800 F. When using an active oxidizing agent, suchas sulfur trioxide, temperatures in the range of -40 F. to 400 F.,preferably 70 F. to 200 F., are used. With less active oxidizing agents,such as. air, higher temperatures are used, such as 100 F. to 800 F.,preferably 375 F. to 575 F. Higher oxidation temperatures result in afaster oxidation reaction. When the oxidizing agent is in the gaseousphase, another yvariable which affects the rate of the oxidationreaction is the partial pressure of the oxidizing agent. Accordingly, asthe pressure at which the oxidation reaction is carried out isincreased, other conassenza ditionsI remaining the same, the oxidationreaction pro ceeds at a faster rate. Therefore, depending upon the rateof oxidation desired, the oxidation reaction is carried out atsub-atmospheric, atmospheric or super-atmospheric pressures. Usually itis preferred to carrylout the oxidation lreaction' at arpressure betweenabout 10 and 100 pounds per square inch absolute, depending upon thecomposition or oxygen content of Ithe oxidizing gas. Lower or higherabsolute pressures may be satisfactorily used, if desired. Loweroxidation pressures are useful, in that they facilitate release andremoval of the more volatile, and other undesirablematerials, eg., H2O,from the reaction mixture.

The rate of oxidation is also dependent upon, and influenced by, thedistribution of the oxidizing gas within the reaction mixture and therate of introduction of the oxidizing Igas thereto. The oxidizing agentis preferably introduced and present in the reaction mixture in a finelydispersed state,in order'to achieve better contact with the materialsundergoing oxidation and better mixing therewith. An increase in therate of introduction of the oxidizing gas, of course, increases the rateof oxidation, other conditions remaining unchanged. The conditions oftemperature, pressure, oxygen content of the oxidizing gas, Arate ofintroduction of oxidizing gas, etc., are correlated, adjusted andcontrolled so as to carry out the oxidation reaction at -a sufficientlyrapid rate so as to minimize reaction time while readily and easilycontrolling the reaction.

Conditions which have been found to be satisfactory .for producing thedetergent of this invention from a selected hydrocarbon fraction, whenusing a moderate oxidizing agent, such as air, are set forth in TableIII.

Exemplary of the inuence of various variables upon the oxidationreaction, it is pointed out that at a tempera-` ture of 482 F. and at anair introduction rate of about 0.32 s.c.f. per pound of oil per hour andat about atmospheric pressure, the oxidation reaction requires about 20hours before the desired degree of completion is reached (as measured byincrease in viscosity). When the air rate was increased to 1.44 s.c.f.per pound of oil per hour, only 16 hours were required to convert theoil to an oxidized product of similar viscosity. Increasing thereactiontemperature to 572 F. decreasedthe time required for oxidationappreciably. Reducing the reaction temperature to below 390 F. increasedthe reaction time under these conditions.

It has been found that the time required for the reac-` tion mixture .toreach the desired degree of oxidation can be decreased or increased bythe -use of catalysts. Positive (promoters) or negative (inhibitors)catalysts can be used to modify the reaction rate and time.

Catalysts which have been found to promote the oxidation reaction andlto decrease the time required for oxidation reaction include the variouswell known oxidation catalysts, such as the oil soluble salts andcompounds containing such metals as copper, iron, cobalt, lead, zinc,cadmium, silver, manganese, chromium, vanadium, and the like, having anatomic number between 5l and 113, inclusive. The naphthenates of thesemetals are particularly useful. Especially useful and outstanding as acatalyst are those compounds which are obtained by reacting a compoundcontaining both phosphorus and sulfur, such as P285, with a terpene,either monocyclic or dicyclic or. a mixture :thereof, such as pinene, asdisclosed in my copending U.S. application, Serial No. 264,839, filedJanuary 3, 1952, now U.S. Patent No. 2,758,069. A particularlyleffective catalyst of this type is widely used as a corrosion inhibitorfor petroleum lubricating oils and is sold under the trade nameSantolube 395-X, and is a P2S5- terpene reaction product. This reactionproduct exhibits a'marked catalytic effect, resulting in a decrease ofseveral hours in the time normally required for the oxidation reactionto reach the desired degree of completion. Also, it is pointed out thatthe above-mentioned metal naphthenates, especially the copper and ironnaphthenates, effectively catalyze the oxidation reaction ata'temperature in the range of 300 to k500 F. Usually, however, thecatalytic effeet of these'metal naphthenates is pronounced for only afew hours and then becomes ineffective, the addition of morenaphthenates being required in order to maintain a catalytic effect uponthe oxidation reaction.

`Negative catalysts or inhibitors, i.e.,materials which tend to increasethe time required for the oxidation reaction, are usually high molecularweight aliphatic alcohols, such as the C to C24 highly branched,non-straight chain and normal aliphatic alcohols. Typical materialuseful as an anti-catalyst or inhibitor is a highly branched octadecylalcohol, such as 2,2,4,5,810,10-heptamethyl5 undecanol and n-octadecylalcohol.

These catalysts can be added in catalytic amounts, usually in the rangeof 0.1 percent to 4.0 percent by Weight of the oil undergoing oxidation,depending upon the catalytic promoting or inhibiting effect desired. Anamount of one of these types of catalyst, such as about 1.0 per-V centby weight of the oil, is sufficient for most purposes. It is pointed outthat the employment of catalysts is beneficial, in that they decrease orincrease the time required for oxidation (for better control) and, insome cases, even improve the quality of the detergent recovered as aproduct from the oxidation reaction. However, the presence of acatalyst, positive or negative,'is not essential' to the practice ofthis invention.

More active oxidizing agents, such as sulfur trioxide, may also be usedin the oxidation step, as pointed out above. When liquid sulfur trioxideis utilized as the oxidizing agent, the reaction is most readily carriedout when both the oil and sulfur trioxide are separately diluted with amodifying solvent. Solvents which maybe utilized in this operation undersuitable temperature conditions include liquid sulfur dioxide, hexane,tetrachloroethylene, ethylene dichloride, pyridine, nitrobenzene anddioxane.

Liquid sulfur trioxide is an extremely reactive compound and, if addeddirectly to the oil, will cause excessive charring and violentsplattering. `It is necessary to moderate this excessive reactivity bydilution with a solvent, such as those disclosed above. A molar ratio ofsolvent to sulfur trioxide of at least about 1:1 appears to benecessary, and it is preferred to use a ratio of 2:1 or greater.Dilution of the oil is also very desirable for the reduction ofviscosity and` to facilitate mixing, but such dilution is not required.Dilution of the oil may be obtained with some non-reactive solvent otherthan that utilized for the dilution of the sulfur trioxide. Use of thesame diluent, however, simplifies the recovery problem. Gaseous S03maybe introduced into the oil directly or mixed with a carrier gas, suchas air, nitrogen or other inert gas. In the case of gaseous S03, anelevated temperature, eg., 200 to 300 C., is frequently used.

The extent of oxidation is determined by the ratio of oil to sulfurtrioxide. The weight ratio may be varied from 1:1 to 30:1, but ispreferably maintained within the range of between 3:1 to 18:1. Ratiosfrom 3:1 to 8:1 are the most desirable. Very low ratios resultv in theuse of excessive amounts of sulfur trioxide without obtaining acorresponding increase in useful product. Very highfratiosfail to obtainsufficient oxidation to, becco-` nomic'al.

TheV initial reaction of the sulfurtrioxide with oil is almostinstantaneous -at room temperature' .or above, but the reactioncontinues for extended periods of'time, ,e.g.,` up to as much as 144hours or more. At highertem-y peratures the time of the slower secondaryreactions is shortened to less than 24 hours. vThe evolution of sul; furdioxide and other gases causes muchyfoaming and the rate of reactionmust be controlled 'sufficiently toI per-v mit the capacity of theapparatus to lhandle the foaming reaction mixture. The time required forVreaction may be shortened to as little asY three minutes, in whichcase, secondary reactions do not take place to,any great extent. Thequality of the :product is notmaterially affected bythe length ofreaction `time or by the absence or occurrence of they secondaryreactions. v

The temperatures which may generally be utilizedin the oxidationreaction, wherein sulfur trioxide `is used as the oxidizing agent, rangefrom 40 to 400 F.,A preferably from 70 P. to' 200 lF. Avery short periodof time, usually less than three hours, is required for the initialreaction. 'I'his time is sometimes ask short as three minutes.

After the reaction, the product is treated,k for the removal of acid andother impurities. Acid is conveniently removed from the product by waterwashing. The product is concentrated in the manner discussed later inconnection with the product obtained ina process utilizing a less activeoxidizing agent.

The detergent produced by sulfur `trioxide oxidation is somewhatimproved in color by reduction. This is preferablyv accomplished bytreatment in alcoholwith lithium hydride or with zinc and hydrochloricacid. Catalytic hydrogenation or chemical reduction can also be used.

kThe extent to which the oxidation reaction is carried out is dependentupon the selected oil fraction being oxidized and the yield of detergentmaterial desired. I have found that if the oil being oxidizedcontains arelatively low concentration of lower molecular weight hydrocarbons, theoil may be oxidized toa considerable extent, up to as high as percent-byweight of the oil charged, without any deleterious effects upon thereaction itself or the detergent product. Also, I havev observed thatwhen the aromatic content of the charge stock is low, such as belowabout 5 percent by weight oflcarbon atoms in aromatic rings andespecially below about 2 percent by weight, the charge stock can beoxidized to a greater extent without any undesirable effects oradversely affecting the yield, such as may happen when there is anappreciable amount, above about 5 percent by weight of aromatic carbonatoms, presentjtherein. In general, the oxidation reactionis carried outuntil the oxidized oil has increased in'viscos'ity, when Vexpressed inSaybolt Universal Seconds (SUS) at210 FQ, from 1.5 to 50 fold,preferably from 1.5 to 10 fold, over that of the originally chargedunoxidized oil. The range 1.5 to 2 fold has been found especiallyvaluable Vwith some stocks. When the oxidation reactionris carried'outto a 3 to 10 fold increase in viscosity, the yield of active detergentrecovered from theroxidized oil amounts to about l5 to 50 percent byweight of the original unoxidized oil. Continued, oxidation, especiallyto yields above about'60 percent, tends to produce a certainamount of'oil-insoluble oxidized materials which,` although they do not adverselyaffect the effectiveness Y,of the'oil-soluble detergent, do adverselyeffect the yield of the desired product. VAlso, since it is oftennecessary to remove these oil-insoluble oxidized materials, it isdesirable, therefore, not `to continue the oxidation reaction beyondthat ,point at' which the oil-insoluble materials are produced. l

In generaLrhowever, the extent to which the selected oil fraction isoxidized in the practice of thisinvention is primarily a. matter ofconvenience,l based on. the lease iication assegna of handling ofreactants and reacted (oxidized)materials,

the' productl recovered (as by propane fractionation o-f theoxidationreactionmixture), if the recovered product is again oxidized toa hard, brittle mass, the reoxidized n'iaterial has a detergent power oractivity, when tested as alubricatingoil additive, by a hereinafterdefined test, in a Lauson engine which simulates the well-known, widelyaccepted L-l diesel engine ftest, only slightly less than the productrecovered from the initial and'rst oxidation reaction. v f l While theviscosity increase measured at SUS at 210 F. has been stated as one wayof determining and measuring the extent of the oxidation reaction, it isnot the only way. Another way is toi' measure the amount vof 'waterproduced during the oxidation reaction. Another method of determiningthe extent of the reaction isto measure the detergent activity of theoxidation reaction mixturfelby' a spot plate test.. Still-another methodis to determine the amount of propane insoluble material presentjin-'the oxidation reaction mixture.` V"When the oxidation reaetion iscompleted tothe'extent'desired, the propane insoluble, oil solublematerial in the reaction ,mixture amounts to between about S'and about60 percent by .Weight of the reaction mixture, more often between aboutand about 40 percent by weight;

The oxidation reactionvmixturc, .after oxidation, can be, used directlywithout additional 'concentration or puri- However, if a product-ofimproved quality, purityand greaterL concentration andeifectiveness perunit weight is desired, the active detergent oil-additive material ispreferably'removed and. recovered from thev oxidation reaction mixture.When the hydrocarbon feed'tothe oxidation reaction is a liquid, `therecovery and concentration of the active additive material is preferably'obtained by propane fractionation, 'such as 'is disclosed by J. MLWhitely and G.' A. Beiswenger in U.S. Patent 2,110,845. l f l#'Following propane fractionation thematerial is a iirm, plastic orslightly brittle -mass soluble in pentane, benzene,

have anvacid number belowabout 50 and asaponitication numberybelowlabout 100.- r

Following-the oxidation, an alkaline earth material, such vas theoxides, hydroxides and carbonates of calcium,.strontium or-barium, isadded. Representative cornpounds include lcalcium oxide, calciumhydroxide, calcium carbonate, barium oxide, barium hydroxide, strontiumhydroxide, and strontium carbonate. This is preferably donebydissolvingl the oxidized material in a suitable solvent, suchas an SAE-10` oil, and adding the alkaline earth compound. Other solvents includearomatics, such as `benzene and toluene. Frequently it is advantageousto add a small amount of a non-solvent, such 'as isopropyl alcohol, inorder to obtain better contacting. This is especially true when anaqueous solution of the alkaline earth material is used. When thealkaline earth hydroxide is used, the hydrate maylikewise be used, .e.,when barium hydroxide is used, the anhydrous material, the monohydrat'e,or the octahydrate, can be used. The alkaline material is added as anaqueous solution or as iinely powdered material, irlV a concentration of0.1 to 20 weight percent, and preferably from 0.5 to l0 weighty percentof the hydrocarbon material. Following addition,the mixture ispreferably stirred for a sufhcient length lof time to insure adequatereaction. The' resulting solution is .filtered to -remove excessalkaline metal material and any other-*insoluble material. Temperaturesfor this reaction usually range from around 50 F. to around 500 F.,although the preferred temperature range is 200 to 300 F. A reactiontime of 5 minutes to 5' hours is usually required. The resultingproduct, after filtration, is au oil concentrate containing theadditive,

diethyl ether and the other usual liquid hydrocarbon solvents. It isalso soluble in `all petroleum lubricating oils, as well as in polymersand polyester synthetic oils. The additive leaves a dark red color, whenrubbed on a white surface and when dissolved in a lubricating oil, suchas a motor oil, gives the oil a black appearance by reflected light. Theoxidized material has a strong tinting power when dissolved inlubricating oil. It has a low acid num-l ber below about 50, expressedasthe number of milli grams of KOH per gram, and a saponil'lcation numberbetween 0 and, about 100. The oxygen content of these materials rangesfrom about 2 percent up to about 10 percent by weight, usually from 3percent to 8 percent, although in some cases the oxygen content maybe ashigh as 15 percent or as low as lpercentby weight.

While these solid oxygen-containing materials v appear to have asupercial resemblance to reSiIlS, asphaltenes and sludges heretoforereported inthe literature,'there l which can be added to any desiredlubricating oil base stock direct, orthe additive may be separated fromthe oil'concentrate. f

1 Another method of preparing these additives is to add the alkalineearthcompound to the hydrocarbon fraction prior to the oxidation step.'In this manner, the additive can be prepared in one step. The physicalconditions of temperature and pressure set forth above for the oxidationare used for the reactionin this case.

This active solid detergent material can be recovered directly from thereaction mixture by solvent extraction with a solventi which isselective for the relatively unoxidized, essentially hydrocarbonmaterial therein, and which solvent is at the same time essentially anon-solvent forthe active detergent material in the reaction mixture.ySuitable solvents for thel'recovery of the solid active detergentmaterial from the oxidized reaction mixture include propane, isopropylalcohol, a solvent mixture of propane with modifying amounts (up toabout 50 percent by weight) of other low boiling hydrocarbons, such asmethane, ethane, and butane. Other selective solvents, such as methylethyl ketone, methyl isobutyl ketone, tertiary butyl alcohol, isobutylalcohol, ethyl acetate, dioxane, morpholine, dimethyl formarnide andphenol, are also useful. In general, those polar compounds containing"only carbon, hydrogen, and oxygen atoms, such as aliphatic alcohols,aliphatic ketones, and esters having from` 3to 8 carbon atoms permolecule, are useful as treating materials in the practice of thisvinvention. `Mixtures of these various materials may be used.

' One step-wise processfor concentrating the detergent materialcomprises 4extracting the partially `oxidized oil with methyl isobutylketone, methyl ethyl ketone, or mixt'uresof thetwo, at appropriatetemperatures so as to dissolve onlyV the oil and lower molecular weightadditive material. The proper temperature will depend'upon the ratio ofsolvents `and the percentage of productrto be dissolved. The undissolvedmaterial is thereafter mechanically separated from the dissolvedmaterial.

' -When these materials are used in obtaining the active detergentmaterial from the oxidized reaction mixture, the active solid detergentis recovered as a propane insoluble, oil soluble, solid phase (rainate),the ineffective,

ll substantially hydrocarbon material of the reaction mixture beingdissolved in the treating material as an extract. rl"he'propane solublephase, from which the active detergent material is separated, has aviscosity index much higher than that of the unoxidized oil. Thispropane soluble phase may beA used toblend with an oil for the purposeof improvingthe viscosity index of that oil. Y

Inythe recovery of t-he active detergent material, it is preferred inthe practice offthis invention to employ propane as a selective solvent,the solid active detergent being recovered as a separate Vpropaneinsoluble phase under propane fractionating conditions of temperature,pressure and ratio of solvent to material being treated (usually :1 to25:1 by volume). The solvent extraction operation for the recovery ofthe active detergent material is usually carried on at a temperature inthe range 50 F. to 250 F., especially'inthe rangeL 100 F. to 160 F., anda pressure of between 200 p.s.i.g. to 500 p.s.i.g. Countercurrentsolvent extraction techniques are usefully employed, as well asmultiple, solvent extraction steps of separately contacting and recoveryof the undissolved active detergent.

VIn many instances, the activity of the detergent material isconsiderably increased by additionally treating thisrecovered soliddetergent material with an aliphatic alcohol, in the C3 to C8 range,such as isopropyl alcohol, and recovering apuried and more activedetergent therefrom as a solid, `alcohol insoluble phase. The alcoholtreatment has a two-fold purpose. Traces of peroxides,

aldehydes, and the like, which may be oxidation promotors, are removedthereby. In addition thereto, it appears that a beneficial chemicalchange takes place during stripping of residual alcohol solvent from theadditive material.

The above-described sequence of recovery and purification steps does notin some instances greatly inuence the quality and effectiveness of thesolid, final detergent product.v It is preferred to employ a propanefractionation step prior to the organic polar compound treating -step toavoid emulsions which are difficult to break and which presentoperational difculties when the alcohol or ketone treating stepprecedesthe propane solvent extrac-V tion step.

The method by 'Whichthe additives of the present invention are formed.,is notfully understood, since the amount of alkalineV earth metalcompound reacting often exceeds by a large factor that corresponding tothe neutralization number. The reaction appears to be quite rapid,indicating the saponilication of ester groups is not thefullexplanation. While not wishing to be bound by any possible theoryset forth, I believe that it may be that chelates or other coordinationcomplexes play an important part. The material preparedfrom theoxidation of the oil in the presence of an alkaline earth metalcompound, such yas barium hydroxide, has excellent detergent properties,as measured by the spot plate test, even when very little viscosityincrease has taken place.` Measurement of the olf-gas indicates thatoxidation is taking place during the reaction even though the viscosityof the oil isy not increasing rapidly.

The oxidation step disclosed herein is similar to that disclosed in mycopending application Serial No. 304,659, filed OctoberlS, 1952, nowabandoned, and reference is made thereto for further details andillustrative examples. The additives of this invention show improvementsover the additives produced according to the method of Serial No.304,659 in certain respects when tested ina paraflinic oil in anengineusing a dirty fuel. p The oil to which the solid active detergentmaterial of this invention is added can be any oil of lubricatingviscosity and, preferably, is a lubricating oil commonly used ininternal combustion engines, such as in the crankcase thereof. Theadditive is usually added to the base lubricating oil in effectivedetergent amounts and gen- Gravity, API

erally comprises between 0.1 -percent to 10 percentV by.

weight of the total lubricating oil composition, but may be as high as25 percent Vfor lextreme service conditions. Usually, however, an amountin the yrange 0.3 percent to 10.0 percent by Weight of the totallubricating oil composition is sufficient. A

The' modified diesel L-l test referredl to in the following` exampleswas carried out for a shorter period of time than the 480 hou-rsprescribed by the full scale diesel L-l test set forth in C.R.C.Handbook 1946 by the Cof ordinating Research Council, Inc., at pages 347and following. The procedure outlined in the C.R.C. Handbook wasmodified as to the specific fuel. In its distillation characteristics,the fuel utilized in the tests set forth in the following examplesv hada percent distillationY of 600 F. to 640 F., a minimum 50percentdistillation of 500 F., andan endpoint of 650 YF. to 690 F. Thesulfur content in the fuel utilized4 had a minimum of .35 percentnatural sulfur and a cetane number of between 40 and 45. The simulatedL-l Lauson engine test, used in connection with the following examples,is described in Motor Oils and Engine Lubrication by Carl W. Georgi atpage 83 and following. TheV operating conditions which were utilized inthe tests of the following exampleshave been modified and are asfollows.

The lubricating oil employed as a base oil in these tests was asolvent-refined Mid-Continent oil of lubricating viscosity and havingthe following characteristics I K `30.3 Viscosity at 210 F. 61.8Viscosity index 98 Neutralization number 0.01

The detergent in selected amounts was added to the base oil and testedin a standard Lauson engine. The test consisted in placing920 `grams of.the base oilc0n taining this detergent in the crankcase of a singlecylinder Lauson gasoline engine. der a 1.2 horsepower` load at 16001-20r.p.m.,'maintain ing a cooling jacket temperature of 300 F., an oiltemperature of 225 F., an air-to-fuel ratio of 13.5 :1, carburetor airat roomv temperature, spark advancefof 25 before top of dead center,andcrankcase vacuum of 1.0 inchof mercury'. Atthe' end vof 60 hoursengineV operation under these conditions, the engine Wasstopped,disassembled, and the piston, crankcase and bearingszwere examined. Thepiston varnish was rated on an arbitrary scale of 0 to 10 withrepresenting a clean or perfect condition and 0 representing thedirtiest condition.

Example I A Mid-Continent oil, solvent refined, and dewaxed,

having a Viscosity of 208 SUS at 210 F'.` Was oxidized.

by passing air into 3440 grams of the oil containing barium hydroxideoctahydrate, equivalent to 2.0 percent barium hydroxide.V The airwasdried, metered and introduced through a porous plate located near thebottom of the oil. The oil containing the barium hydroxide was heated to482 F. and treated for 20.4 hours with approximately 0.95 cc. of air pergram of oil per minute. The viscosity of the oil after oxidation wasl648 SUS at 210 F. The oxidized oil containing barium was extracted withliquid propane at 123 F. and 250 p.s.i.g., using a propane to oil ratioof 6:1. The propane insoluble portion represented 36 percent by weightof the oil.

Example Il EVALUATION 0F ADDITIVES The modified diesel L-l test referredto in this and other examples was car-riedV out for a period of 60 orhours, as indicated, instead of thev 480 hours prescribed by the' fullscale diesel L-l test set forth in C.R.C.

The engine was operated un-V tained'in the 60 hour dies'eltest:

v"itove insolubles.

13 Handbook 1946 by the Coordinating Research Council, Inc., at pages347 and following, and as givenin application Serial No. 304,659, page25. 'In the 60-hour tests, a 1.0 percent sulfur fuel was used instead ofthe 0.4 percent used in the 120 hour test.v y A 5 percent blend was`made of barium detergent (prepared as described in Example I) in thebase oildescribed in the above paragraphs. 1.25 percent of Lubrizol 309,a commercial antioxidant containing zinc dithiophosphate, was also addedto the `base oil. The following results werel obtained in the dieseltests:

120 Hour 60 lour Diesel Test Diesel Test 9o. 1 l sa. 7 95. o

Example III PREPARATION OF ADDITIVES To a 50-gallon horizontal still waslcharged 340 pounds of a Mid-Continent oil, solvent refined and dewaxed,having a viscosity of 208 SUS at 210 F. This direct red, batch still wasequipped with 'a 1A" stainless steel tubing containing M6" holes at 3inch intervals-for air distribution. The oil Awas heated to 482"v .atatmospheric pressure and then oxidized bypassing air through the mass at14 standard cubic feet per minute for: a total of 7 hours. The viscosityof the resulting oxidized'oil Was 650 SUSat 210 F. v`

yThe resulting oxidized oil (305 pounds) was transferred to an open top.steam jacketed tank, heated to 170"l F. and 9.25 pounds of nely ground(in a hammer mill) barium hydroxideY octohydrate wasaddd while theoxidized oilwas being agitated. Two hours were allowedfor .the reaction.The barium treatedoxidized oil was filtered .using a horizontal plateSparkler Filtermaintained at about 325 F. The total vfiltrate weighed293 pounds. The viscosity-of the ltratewas 2740 SUS at 210 F.IThefbarium treated oxidized oil-was extracted by the batch method Vwithl lvolumes of isobutane for' l volume of the treated oil at 123 F. Ayieldv of 30 percent insoluble material was obtained. This material wasdifcultly soluble in oill and had a sulfated ash equivalent to '6.8 perfcent barium hydroxide.

Example 1V EVALUATION OF ADDITIVE A 5 percent blend was made of theisobutane-insoluble fraction of thebarium treated oxidized oil (preparedas described in 'Example III) in the base oil described in Example II.v1.25 percentof Lubrizol 309', a commercial anti-oxidant containing zincdithiophosphate, was also added t'o the'base oil. The' following resultswere job- Overall rating `86.8 Lacquer :rating Y 78.9 Carbon 'rating 93-EJamplaV 820 grams of an ashless'. detergent,vprepared by air oxidationat 482v F. and '25 p.s.i.g., followed by propane fractionation, asdescribed in application Serial No. 304,659, was placed in'a containerand dissolved in 1400 ml. of benzene and 120 ml. of isopropyl alcohol.-Thirtyeight grams of barium hydroxide octohydrate was added, which is2.5 weight percent of the additive calculated as Ba(OH)2. The mixturewas warmed just below boiling for one hour and then heated to azeotropeoi the water and alcohol. Fresh portions of benzene were added to Ikeepthe material in solution. After the complete removal of the water, thesolution was centrifuged to' re- A weighed amount of oil was added tofan sludge formation, etc.

14 the solution and the benzeneflashed olf. This product gave thefollowing results in the L-l 60 hour high sulfur fuel test using 1.25percent Lubrizol 309 inhibitor, a commercial, antioxidant containingzinc dithiophosphate. For comparisomthevalue for the untreated ashlessdetergent is'also presented.

r Treated Piston `Rating Percent ywith Concentration B a(OH)z ,i OverallLacquer Carbon 5.0 Nn 89. 3 83. 3 93. 0 2 s l l YM 89.0 s3. 9 91. 4 5.0Yes 92.0 91.2 89.0

' These results indicate that a 2.5 percent concentration of thebariumhydroxidevtreated detergent is 'as effective as a 5.0 percentblend ofthe ashless detergent. A5 percent blend of the treated detergentshowed a very sub- Vstantially improved lacquer rating. The ash contentof the additive is about 2.8 percent, which amounts to only 0.14 percentash in a 5 percent blend.

Example Vl A quantity of ashless detergent was prepared according to themethod of application Serial No. 304,65'9 by oxidizing a finished 250stock having a viscosity of 205 SUS at 210 F., using a temperature of485 F. to 500 F.anda pressure of approximately 25 p.s.i.g. for 7 to 14hours with airas the oxidant. This fshless detergent was .dissolvedfinarnixture of benzene and a small amount of isopropyl'alcohol, and acalculated amount of the barium hydroxide dissolved in Water was addedto the solution. The mixture was heated at"l40f to 160 F. for an hour.The water and alcohol were then removed as an razeotrope and the benzenesolution centrifuged to remove the insoluble material. The solution wasithen lmixed with oil and thebenzene evaporated.V

The results'of modiiied EX-2 tests, described below, with theseadditives, are found inthe following table. All tests were made'using1.25 percent Lubrizol 309, `a commercial antioxidant containing zincdithiophosphate and-SAE 30 oil with 'l0 percent concentration of theadditive, with the exception Athat the additive treated with 2.5 percentBa(OH)2 was usedk in a l1 percent concentration.; i..

The one digit ratings are from 0 to l0 and the two digit ratingsare-0-to 50, the higher numbers being perfect. The -fuel used was athermally cracked dirty-type test fuel.

The 'EX-2 testv is designed to give accelerated low temperature'-s'ludge'conditions ofa type-found in city delivery service. The pistonrings of the Chevrolet engine were slotted -rto allow a large vamountofblow-by'products to enter the oil and a dirty fuel is used. The testisof 96 hours duration and, at the end of this period, the engine israted'for Acleanliness and the oil for viscosity increase,

Under these conditions, the ashlessy detergent without further treatmentconsistently caused an excessive thickening of the crankcase oil.

The product' obtained by treating the ashless detergent with 2.5 percentBa(OH)2 showed a great improvement over the ashless detergent. Unlikethe other samples tested, this additive, in a paraiiinic Ioil and with adirty fuel, produced no crackcase ,geL

Example V11 800 grams of the ashless detergent prepared as described inExample VI was dissolved in'1200 ml. of benzene and 100 ml. of isopropylalcohol. To this mixture was added amounts of various bases equivalentto 2.5 weight percent of barium hydroxide inA about 70 ml. of Water. Themixture was heated belowthe boiling point for 1.5 hours and then thealcohol and water were removed as an azeotrope. The solution wascentrifuged to remove the insolubles. The solution was diluted with SAE20 oil. The benzene was evaporated, leavingthe product.

The results of the L-l 60 hour thigh sul'fur'fuelV engine tests arepresented in the following table. All of the materials were tested atpercent-.concentration with 1.25 percent Lubrizolf309.

Piston Rating l Average of four tests.

2 Equal to 2.5 percent Ba(OH)2 on a gram-equivalent basis. Y

The data in this example show that treating with alkali metal hydroxidesdoes not result in the improvement shown when using alkaline earth metalhydroxides.

Example VIII Solvent refined 250 lubricating oil was'agitated withanequal volume of 32 to 34 percent nitric acid at a temperature of 140 to160-F. for 4 to 12 hours. The oil was separated, washed with cold water,andthendissolved in pentane. The emulsion was broken by the addition ofisop ropyl alcohol.' Pentane was evaporated and a dark red `oilrecovered.. 150 grams of this material was heated lto 212 F., 3375 gramsof Ba(OH)2-I-I2O were added and the mixturev heated forjone hour at thistemperature. Thereafter, the :temperature was raised to 300 F. for anadditional hour. The material, when cooled, was dissolved-in pentane,centrifuged, and the solvent evaporated. The results of a Lauson enginetest made with 1.75 percent concentration of the additive and 0.82percent Santolube-395-X inhibitor, a commercial inhibitor containingP285 reacted terpene with a control comprising the base oil appears inthe following table.

Material tested: Piston varnish Base oil 6.3 Base oil with aboveadditive 8.0

In the above examples, the mixtures were agitated in order to keep thealkaline earth compounds in suspension, since these materials, which arepowders, tend to settle out of the solution instead ofremainingum'formly dispersed and in good contact with the oil.- In thedrawing which accompanies and forms a part of this disclosure, I haveillustrated apparatus for preparingthe detergents of this invention,this apparatus taking advantage of the fact thatrau oxidized oilpercolating'over an alkaline earth metal hydroxide reacts with'thematerial `to form the additive. l j

This apparatus comprises an elongated vessel providedwith an o'il inlet11 and a gaseous material outlet 12 in the upper end portion thereof.Vessel 10 is iilled with an inert granular support 13,7; such asbauxite, on which has been deposited the desired basic material, such asan alkaline earth metal hydroxide, oxide, or carbonate. Heat exchangers14, 16 and 17 are positionedwithin this bed in order to maintain `thetemperature desired for treatment. Means for introducing gaseousmaterial f. is provided in a lower pontion of vesselr 10, thisbeingintror'16 duced through line18 to a perforated plate'19, or otherequivalent gas distribution means.

Conduit 21 communicates with the lower portion of vessel 10 and extendsto the central or upper portion of liquidliquid extraction zone 22. Fromthe lower end portion of zone 22, conduit 23 extends to fractionator-Z,this fractionatorfbeing provided with conduit 26 extending from thelower portion thereof. Extending from the upper end portion ofk zone 22there is provided conduit `27 which communicates with fractionator 28,this fractionator 28 being provided with conduit 29 extending from thelower end portion thereof. Conduit 31 extends from the upper portion offractionator 24to the lower end portion of extraction zone 22 andconduit 32 extends from the upper portion of fractionator 28 to conduit31. Make-up sol: vent can be added throughrconduit 33.*V n n In theoperation of this apparatus, the oil to be oxidized is introducedthrough conduit 11 into the upper portion of vessel 10, this vesselbeinglilled with the treating material: The oil passes downwardly overthis granular treating material 13 countercurrent to the flow of oxidantintroduced throughdistribution means 19. The oil is added at such a"rate that it is oxidized to the desired extent by the time `it leavesVessel 10, it being removed through conduitk 21. The use of thisapparatus provides continuous movement downwardly over the treatingmaterial with a minimum of mixing of the various portions of the oil, asituation that is 'dicult to avoid when batch-wise operation isutilized.v Since. the specic ,gravity of the oxidized maferial is higherthan that of the' charge oil, the tendency of these materials to mixisminimized. For instance, with one particular .oil, the oxidized materialhad a specific gravity of 0.93 compared to 0.87 for the charge oil.

The apparatus shown in this drawing includes the propane fractionationstep which is preferred in the recovery of the additive. The treated oilis introduced by conduit 21` intoliquid-liquid extraction zone 22 andconduit 31 supplies 'solvent thereto. Although the treated oil andsolvent'canbe introduced at a common point I prefer to operate byintroducing `the oil into the central or upper portion of zone 22 and bysupplying the solvent to the lower portion, as shown, in order toprovide countercurrent extraction. Temperatures for the'` oxidation havebeen previously recited. Temperatures inthe extraction zone can varywidely. below the critical temperature with liquid phase conditions.Using propane as the solvent, a suitable range for the bottom of thezone isV to 150 F., preferably about F., and the range of 125 to 200 F.,preferably about l50 F., for the top of the zone. The nonsoluble portionof the treated stock, being heavier, is' re-v moved from the lowerportion of zone 22, conveyed by line 23 to frctionator 24, where thesolvent dissolved therein is returned to the process Vthrough overhead'conduit 31 and the additive is recovered as a bottomproductin conduit26. The rpropane soluble portion, the upper layer found in the zone- 22,is passed to fractionator 28 through'conduit 27,- where the propaneisrecovered and returned1 to the system through line 32 and theunoxidized portion is recovered in conduit 29. This portion can bereturned to the treating column 10, as desired, or'usedfor otherpurposes.

As many possible embodiments may be made 'of' this invention withoutdeparting-from `the spirit and scope thereof, it is to be understoodthat all matter herein set forth or shown in the accompanying drawing isto be interpreted as illustrative and not in a limiting sense.

I claim:

l. A process for producing a material having detergent and dispersantproperties which comprises subjecting a hydrocarbon fraction, having a.refractive index m32 of between 1.440 and 1,520, a minimum'molecularweight of 450, a viscosity of at leastl 50 SUS at 210 F., a viscosityindex (when deetrminable) at at least 50, and an average It' ispreferred to operate' carbon atom content per molecule of at least 40,to oxidation with air at a temperature of 100 F. to 800 F. for a time of3 to 75 hours and at a pressure of 10 to 200 p.s.i.a., said air beingsupplied at a rate of 0.01 to 3.0 cf. per hour per pound of saidhydrocarbon, recovering the oxidized fraction of said hydrocarbon bysolvent extraction, adding to said oxidized portion 0.1 to 20 percent byWeight of at least one compound selected from the group consisting ofalkaline earth hydroxides, oxides, and carbonates, heating said mixtureat a temperature in the range of 50 to 500 F. for a time of 5 minutes to5 hours, and recovering the resulting treated material, said materialhaving detergent and dispersant properties in lubricating oilcompositions.

2. The process of claim 1 in which said alkaline earth material isbarium hydroxide.

3. The process of claim 1 in which said alkaline earth material iscalcium hydroxide.

4. The process of claim 1 in which said alkaline earth material isbarium oxide.

5. The process of claim 1 in which said alkaline earth material iscalcium oxide.

6. A process for producing a material having detergent and dispersantproperties which comprises subjecting a hydrocarbon fraction, having arefractive index m32 of between 1.440 and 1.520, a minimum molecularWeight of 45o, s viscosity of st least 5o sUs at 210 F., s viscosityindex (when determinable) of at least 50, and an average carbon atomcontent per molecule of at least 40, to oxidation in the presence of anoxidizing agent under oxidizing conditions and at least one compoundselected from the group consisting of alkaline earth hydroxides, oxides,and carbonatos, said oxidation being suicient to provide at least a 1.5fold increase in viscosity, and recovering a resulting material havingdetergent and dispersant properties when used in a lubricating oil.

7. A lubricant composition comprising a major portion of lubricating oiland at least 0.1 percent by weight of an oil soluble materialhavingdetergent and dispersant properties, said material produced by oxidationand treatment with at least one compound selected from the groupconsisting of alkaline earth hydroxides, oxides and carbonates, of ahydrocarbon fraction having a refractive index nD20 of between 1.440 and1.520, an' average molecular weight of at least 550 and no appreciableportion thereof having a molecular weight below 450, a viscosity of atleast 50 SUS at 210 F., a viscosity index (when `18 determinable) of atleast 50, and an average carbon atom content per molecule of at least40, the solid oxidation product having an acid number below 50, asaponication number in the range of 0 to 100, and an oxygen content inthe range of 1 tok 15 percent by weight.

8. The composition of claim 7 in which said material having detergentand dispersant properties is present in an amount from'0.3 to 10.0 partsby weight.

9. A lubricant composition comprising a major portion of lubricating oiland at least 0.1 percent by weight of an oil-soluble material havingdetergent and dispersant properties, said material produced by oxidationand treatment With at least one compound selected from the groupconsisting of alkaline earth hydroxides, oxides, and carbonates, of ahydrocarbon fraction having a refractive index 111,20 of between 1.480and 1.515, an average molecular weight of at least 600 and noappreciable proportion thereof having a molecular weight below 400, aviscosity of at least SUS at 210 F., a viscosity index (whendeterminable) of at least 80, and an average carbon content per moleculeof at least 50, the solid oxidation product having an acid number below50, a saponication number in the range of 0 to 100, and an oxygencontent in the range of 1 to 15 percent by weight.

10. The composition of claim 9 wherein said alkaline earth material isbarium hydroxide.

References Cited in the le of this patent UNITED STATES PATENTS pag'es87, 91 and 92.

Performance of Lublicating Oils, Zuidema, Reinhold Pub. Co., 1952, page123.

1. A PROCESS FOR PRODUCING A MATERIAL HAVING DETERGENT AND DISPERSANTPROPERTIES WHICH COMPRISES SUBJECTING A HYDROCARBON FRACTION, HAVING AREFRACTIVE INDEX ND20 OF BETWEEN 1.440 AND 1.520, A MINIMUM MOLECULARWEIGHT OF 450, A VISCOSITY OF AT LEAST 50 SUS AT 210*F., A VISCOSITYINDEX (WHEN DEETRIMINABLE) AT AT LEAST 50, AND AN AVERAGE CARBON ATOMCONTENT PER MOLECULE OF AT LEAST 40, TO OXIDATION WITH AIR AT ATEMPERATURE OF 100*F. TO 800*F. FOR A TIME OF 3 TO 75 HOURS AND AT APRESSURE OF 10 TO 200 P.S.I.A., SAID AIR BEING SUPPLIED AT A RATE OF0.01 TO 3.0 CF. PER HOUR PER POUND OF SAID HYDROCARBON, RECOVERING THEOXIDIZED FRACTION OF SAID HYDROCARBON BY SOLVENT EXTRACTION, ADDING TOSAID OXIDIZED PORTION 0.1 TO 20 PERCENT BY WEIGHT OF AT LEAST ONECOMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKALINE EARTHHYDROXIDES, OXIDES, AND CARBONATES, HEATING SAID MIXTURE AT ATEMPERATURE IN THE RANGE OF 50 TO 500*F. FOR A TIME OF 5 MINUTES TO 5HOURS, AND RECOVERING THE RESULTING TREATED MATERIAL, SAID MATERIALHAVING DETERGENT AND DISPERSANT PROPERTIES IN LUBRICATING OILCOMPOSITIONS.
 6. A PROCESS FOR PRODUCING A MATERIAL HAVING DETERGENT ANDDISPERSANT PROPERTIES WHICH COMPRISES SUBJECTING A HYDROCARBON FRACTION,HAVING A REFRACTIVE INDEX ND20 OF BETWEEN 1.440 AND 1.520, A MINIMUMMOLECULE WEIGHT OF 450, A VISCOSITY OF AT LEAST 50 SUS AT 210*F., AVISCOSITY INDEX (WHEN DETERMINABLE) OF AT LEAST 50, AND AN AVERAGECARBON ATOM CONTENT PER MOLECULE OF AT LEAST 40, TO OXIDATION IN THEPRESENCE OF AN OXIDIZING AGENT UNDER OXIDIZING CONDITIONS AND AT LEASTONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKALINE EARTHHYDROXIDES, OXIDES, AND CARBONATES, SAID OXIDATION BEING SUFFICIENT TOPROVIDE AT LEAST A 1.5 FOLD INCREASE IN VISCOSITY, AND RECOVERING ARESULTING MATERIAL HAVING DETERGENT AND DISPERSANT PROPERTIES WHEN USEDIN A LUBRICATING OIL.
 7. A LUBRICANT COMPOSITION COMPRISING A MAJORPORTION OF LUBRICATING OIL AND AT LEAST 0.1 PERCENT BY WEIGHT OF AN OILSOLUBLE MATERIAL HAVING DETERGENT AND DISPERSANT PROPERTIES, SAIDMATERIAL PRODUCED BY OXIDATION AND TREATMENT WITH AT LEAST ONE COMPOUNDSELECTED FROM THE GROUP CONSISTING OF ALKALINE EARTH HYDROXIDES, OXIDESAND CARBONATES, OF A HYDROCARBON FRACTION HAVING A REFRACTIVE INDEX ND20OF BETWEEN 1.440 AND 1.520, AN AVERAGE MOLECULAR WEIGHT OF AT LEAST 550AND NO APPRECIABLE PORTION THEREOF HAVING A MOLECULAR WEIGHT BELOW 450,A VISCOSITY OF AT LEAST 50 SUS AT 210*F., A VISCOSITY INDEX (WHENDETERMINABLE) OF AT LEAST 50, AND AN AVERAGE CARBON ATOM CONTENT PERMOLECULE OF AT LEAST 40, THE SOLID OXIDATION PRODUCT HAVING AN ACIDNUMBER BELOW 50, A SAPONIFICATION NUMBER IN THE RANGE OF 0 TO 100, ANDAN OXYGEN CONTENT IN THE RANGE OF 1 TO 15 PERCENT BY WEIGHT.